Process for preparing ether-capped poly(oxyalkylated) alcohol surfactants

ABSTRACT

A process for preparing an ether-capped poly(oxyalkylated) alcohol surfactant which results in the absence of metallic catalyst component residues from the ether-capped poly(oxyalkylated) alcohol surfactant.

This Application claims the benefit of PCT application No. US99/25944,published as WO 00/27903 filed on Nov. 3, 1999, which in turn claims thebenefit of U.S. Provisional Application Ser. No. 60/131,409 filed onApr. 28, 1999, (now abandoned), which in turn claims the benefit of U.S.Provisional Application No. 60/107,170, filed on Nov. 5, 1998, (nowabandoned).

TECHNICAL FIELD

The present invention relates to an industrial process for preparinglow-foaming nonionic surfactants and more particularly to a process forpreparing ether-capped poly(oxyalkylated) alcohol surfactants which havesuperior spotting and filming benefits in dishwashing and hard surfacecleaning applications, as well as suds suppression in detergentcompositions.

BACKGROUND OF THE INVENTION

Ether-capped poly(oxyalkylated) alcohols can be prepared using variouscatalysts, such as Lewis acids. However, for industrial production,metallic catalysts, such as stannic chloride is preferred. In additionto being an excellent catalyst for the reaction of a glycidyl ether withethoxylated alcohol, metallic catalysts are economical and readilyavailable in commercial bulk quantities. They also offer safety and easeof handling advantages on an industrial scale versus alternativecatalysts. One important disadvantage for metallic catalysts is that thesoluble metallic residue component of the catalyst, such as tin residueswhen is the catalyst SnCl₄, resulting from there use as reactioncatalyst, generally cannot be tolerated above about 100 ppm in manycleaning formulations and applications and these residues are difficultand expensive to remove from ether-capped poly(oxyalkylated) alcoholcompositions. Successful laboratory approaches to removal of residualmetallic catalyst component, such as the use of a silica gel plug andeluting with a 5% methanol in dichloromethane solution leads tocomplexity and high cost on an industrial production scale. Due to thesurfactant properties of the ether-capped poly(oxyalkylated) alcohol,water washing for metallic catalyst component removal leads toemulsification problems leading to complex organic—aqueous separations.

Consequently, the problem remains that there is no commercially viableor industrial scale process for the removal of these metallic catalystcomponent residues from the ether-capped poly(oxyalkylated) alcoholcompositions.

BACKGROUND ART

U.S. Pat. No. 4,272,394, issued Jun. 9, 1981, U.S. Pat. No. 5,294, 365,issued Mar. 15, 1994 U.S. Pat. No. 4,248,729, issued Feb. 3, 1981; U.S.Pat. No. 4,284,532, issued Aug. 18, 1981; U.S. Pat. No. 4,627,927,issued Dec. 9, 1986; U.S. Pat. No. 4,790,856, issued Dec. 13, 1988; U.S.Pat. No. 4,804,492, issued Feb. 14, 1989; U.S. Pat. No. 4,770,815,issued Sep. 13, 1989; U.S. Pat. No. 5,035,814, issued Jul. 30, 1991;U.S. Pat. No. 5,047,165, issued Sep. 10, 1991; U.S. Pat. No. 5,419,853,issued May 30, 1995; U.S. Pat. No. 5,294,365, issued Mar. 15, 1994; GBApplication No. 2,144,763, published Mar. 13, 1985; GB Application No.2,154,599, published Sep. 9, 1985; WO Application No. 9,296,150,published Apr. 16, 1992; WO 94/22800, published Oct. 13, 1994, WO93/04153, published Mar. 4, 1993, WO 97/22651, published Jun. 26, 1997,EP Application No. 342,177, published Nov. 15, 1989 and “GlycerylBisether Sulfates. 1: Improved Synthesis” Brian D. Condon; Journal Ofthe American Chemical Society, Vol. 71, no. 7 (July 1994).

SUMMARY OF THE INVENTION

A process for removing metallic catalyst component residues from theether-capped poly(oxyalkylated) alcohol reaction product has beendiscovered that is simple and economical to practice on an industrialscale. It has been discovered that selected aqueous solutions can beused to effectively extract the metallic catalyst component residuesfrom ether-capped poly(oxyalkylated) alcohol while avoiding oil andwater phase emulsification. This extraction method of purificationavoids organic solvents, costly process aids, process complexity andprovides a simple, economic industrial route to remove the metalliccatalyst component residues in ether-capped poly(oxyalkylated) alcoholsto below about 100 ppm. This residue extraction can be carried out aseither a batch or continuous process. Furthermore, the residue can beremoved in a single or multiple extraction steps.

In accordance with a first aspect of the present invention, a processfor preparing an ether-capped poly(oxyalkylated) alcohol surfactant isprovided. The surfactant has the formula:

R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

wherein R¹ and R² are linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from about 1 to about30 carbon atoms; R³ is H, or a linear aliphatic hydrocarbon radicalhaving from about 1 to about 4 carbon atoms; x is an integer having anaverage value from 1 to about 30, wherein when x is 2 or greater, R³ maybe the same or different, independently H, or C₁ to C₄ in any givenmolecule, further wherein when x is 15 or greater and R³ is H andmethyl, at least four of R³ are methyl, further wherein when x is 15 orgreater and R³ includes H and from 1 to 3 methyl groups, then at leastone R³ is ethyl, propyl or butyl, further wherein R² can optionally bealkoxylated, wherein said alkoxy is selected from ethoxy, propoxy,butyloxy and mixtures thereof. The process comprises the steps of:

(a) providing a glycidyl ether having the formula:

wherein R² is defined as above;

(b) providing an ethoxylated alcohol having the formula:

wherein R¹, R³ and x are defined as above; and

(c) reacting the glycidyl ether with the ethoxylated alcohol to form thesurfactant in the presence of a metallic catalyst;

(d) said surfactant is sparged with an inert gas, preferably N₂, Ar andmixtures thereof, optionally under vacuum, preferably a vacuum in therange of 5 to 500 mmHg; and

(e) extracting said catalyst from said surfactant by at least oneaqueous extraction with an aqueous solution, wherein said aqueoussolution is selected from the group consisting of a from about 2% toabout 15% by weight aqueous solution of sodium carbonate, a from about2% to about 10% by weight aqueous solution of potassium carbonate, afrom about 1% to about 22% by weight aqueous solution of sodium sulfate,a from about 2% to about 6% by weight aqueous solution of sodiumbicarbonate, a from about 1% to about 10% by weight aqueous solution ofpotassium sulfate, a from about 2% to about 24% by weight aqueoussolution of potassium bicarbonate, and mixtures thereof; and whereinsaid surfactant, after said at least one aqueous extraction, containsless than about 100 ppm of the metallic component of said metalliccatalyst.

R¹ and R² are preferably a linear or branched, saturated or unsaturated,aliphatic hydrocarbon radical having from about 6 to about 22 carbonatoms and x is an integer having an average value of from about 6 toabout 15.

The step of reacting the glycidyl ether with the ethoxylated alcohol ispreferably conducted at a temperature of from about 50° C. to about 95°C. with 60° C. to about 80° C. even more preferred when Lewis acidcatalysts are employed.

The step of providing the glycidyl ether may further comprise the stepof reacting a linear aliphatic or aromatic alcohol having the formulaR²OH and an epoxide having the formula:

wherein R² is defined as above and X is a leaving group. This reactionmay also be conducted in the presence of a catalyst as defined above.The catalyst is typically employed at levels of about 0.1 mol % to about2.0 mol % and the reaction is preferably conducted in the absence of asolvent at temperatures of from about 40° C. to about 90° C.

As already noted, the surfactants have advantages, including superiorspotting and filming reduction benefits as well as excellent greasy soilremoval, good dishcare, suds suppression and good overall cleaning.

Accordingly, it is an aspect of the present invention to provide aprocess for producing a low-foaming nonionic surfactant having superiorspotting and filming reduction benefits as well as excellent greasy soilremoval, good dishcare, suds suppression and good overall cleaning. Itis a further aspect of the present invention to provide a process forproducing an ether-capped poly(oxyalkylated) alcohol surfactant. It is afurther aspect of the present invention to provide a low-foamingnonionic surfactant produced by the process of the present invention.These and other aspects, features and advantages will be apparent fromthe following description and the appended claims.

In the description of the invention various embodiments and/orindividual features are disclosed. As will be apparent for the skilledpractitioner all combinations of such embodiments and features arepossible and can result in preferred executions of the invention.

All parts, percentages and ratios used herein are expressed as percentweight unless otherwise specified. All documents cited are, in relevantpart, incorporated herein by reference.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Once again, the present invention is directed toward a process forproducing a low-foaming nonionic surfactant for use in detergentcompositions.

The novel surfactants of the present invention comprise ether-cappedpoly(oxyalkylated) alcohols having the formula:

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

wherein R¹ and R² are linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from about 1 to about30 carbon atoms; R³ is H, or a linear aliphatic hydrocarbon radicalhaving from about 1 to about 4 carbon atoms; x is an integer having anaverage value from 1 to about 30, wherein when x is 2 or greater R³ maybe the same or different and k and j are integers having an averagevalue of from about 1 to about 12, and more preferably 1 to about 5,further wherein when x is 15 or greater and R³ is H and methyl, at leastfour of R³ are methyl, further wherein when x is 15 or greater and R³includes H and from 1 to 3 methyl groups, then at least one R³ is ethyl,propyl or butyl, further wherein R² can optionally be alkoxylated,wherein said alkoxy is selected from ethoxy, propoxy, butyloxy andmixtures thereof.

R¹ and R² are preferably linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon radicals having from about 6 to about22 carbon atoms with about 8 to about 18 carbon atoms being mostpreferred. Additionally, R² may be selected from hydrocarbon radicalswhich are ethoxylated, propoxylated and/or butoxylated. H or a linearaliphatic hydrocarbon radical having from about 1 to about 2 carbonatoms is most preferred for R³. Preferably, x is an integer having anaverage value of from about 1 to about 20, more preferably from about 6to about 15.

As described above, when, in the preferred embodiments, and x is greaterthan 2, R³ may be the same or different. That is, R³ may vary betweenany of the alkyleneoxy units as described above. For instance, if x is3, R³may be selected to form ethyleneoxy (EO) or propyleneoxy (PO) andmay vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO);(PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the integerthree is chosen for example only and the variation may be much largerwith a higher integer value for x and include, for example, multiple(EO) units and a much small number of (PO) units. However, when x is 15or greater and R³ is H and methyl, at least four of R³ are methyl,further wherein when x is 15 or greater and R³ includes H and from 1 to3 methyl groups, then at least one R³ is ethyl, propyl or butyl.

Particularly preferred surfactants as described above include those thathave a low cloud point of less than about 20° C. These low cloud pointsurfactants may then be employed in conjunction with a high cloud pointsurfactant as described in detail below for superior grease cleaningbenefits.

Most preferred according to the present invention are those surfactantswherein k is 1 and j is 1 so that the surfactants have the formula:

R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

where R¹, R² and R³ are defined as above and x is an integer with anaverage value of from about 1 to about 30, preferably from about 1 toabout 20, and even more preferably from about 6 to about 18. Mostpreferred are surfactants wherein R¹ and R² range from about 9 to about15, R³ is H forming ethyleneoxy and x ranges from about 6 to about 15.

Basically, the alcohol surfactants of the present invention comprisethree general components, namely a linear or branched alcohol, analkylene oxide and an alkyl ether end cap. The alkyl ether end cap andthe alcohol serve as a hydrophobic, oil-soluble portion of the moleculewhile the alkylene oxide group forms the hydrophilic, water-solubleportion of the molecule.

It has been surprisingly discovered in accordance with the presentinvention that significant improvements in spotting and filmingcharacteristics and, when used in conjunction with high cloud pointsurfactants, in the removal of greasy soils relative to conventionalsurfactants, are provided via the ether-capped poly(oxyalkylene) alcoholsurfactants of the present invention.

It has been surprisingly discovered that the ether-cappedpoly(oxyalkylene) alcohol surfactants of the present invention inaddition to delivering superior cleaning benefits also provide good sudscontrol. This suds control can be clearly seen in the presence of highsudsing surfactants, such as amine oxides, or in the presence of highsudsing soils, such as proteinaceous or egg soils.

Generally speaking, the ether-capped poly(oxyalkylene) alcoholsurfactants of the present invention may be produced by reacting analiphatic alcohol with an epoxide to form an ether which is then reactedwith a base to form a second epoxide. The second epoxide is then reactedwith an alkoxylated alcohol to form the ether-capped poly(oxyalkylene)alcohol surfactants of the present invention. The product of the processis a purified mixture of ether-capped poly(oxyalkylene) alcoholsurfactants. The present invention is also directed to the product,namely the purified mixture of ether-capped poly(oxyaLkylene) alcoholsurfactants produced by the present method.

The process comprises the first step of providing a glycidyl etherhaving the formula:

where R² is defined as above. Various glycidyl ethers are available froma number of commercial sources including the Aldrich Chemical Company.Alternatively, the glycidyl ether may be formed from the reaction of alinear or branched, aliphatic or aromatic alcohol of the formula R²OHwhere R² is defined as above and an epoxide of the formula:

where X is a suitable leaving group. While a number of leaving groupsmay be employed in the present invention, X is preferably selected fromthe group consisting of halides including chloride, bromide, and iodide,tosylate, mesylate and brosylate, with chloride and bromide being evenmore preferred with chloride being the most preferred (e.g.epichlorohydrin).

The linear or branched alcohol and the epoxide are preferably reacted atratios ranging from about 0.5 equivalents alcohol to 2.5 equivalentsepoxide with 0.95 equivalents alcohol to 1.05 equivalents epoxide moretypical under acidic conditions for catalysis purposes. The catalyst isa metallic catalyst. The term “metallic catalyst”, includes within itsdefinition catalysts which include a metallic a component. Thisdefinition includes both salts, such as AlCl₃, etc., and covalentcompounds, such as BF₃, SnCl₄, etc., which include a metallic component.The metallic component includes all elements commonly know as metals,such as alkali metals, alkaline earth metals, transition metals, andBoron.

Suitable catalysts include, but are not limited to, TiCl₄, Ti(O^(i)Pr)₄,ZnCl₂, SnCl₄, SnCl₂, FeCl₃, AlCl₃, and mixtures thereof, more preferablySnCl₄. The metallic catalyst are preferably Lewis acids. Suitable Lewisacid catalysts include, but are not limited to, SnCl₄, BF₃, AlCl₃, andmixtures thereof. The metallic components of these preferred catalystsare Ti, Zn, Fe, Sn, B, and Al. The metallic Lewis acid, are preferablyemployed at amounts of about 0.1 mol % to about 2.0 mol % with about 0.2mol % to about 1.0 mol % being more typical.

While the reaction may be conducted in the presence of a suitablesolvent such as benzene, toluene, dichloromethane, tetrahydrofuran,diethylether, methyl tert-butylether or the like, the reaction ispreferably conducted neat or in the absence of solvent.

Lastly, the reaction is conducted at temperatures preferably rangingfrom about 40° C. to about 90° C., more preferably from about 50° C. toabout 80° C.

Before the extraction of the catalyst from the surfactant, thesurfactant is either sparged with an inert gas, preferably, nitrogen,argon or mixtures thereof or placed under a vacuum, to remove anyoxygenated impurities which were formed during the reaction. Theseimpurities are those typically associated with any ethoxylationprocesses, such as ethanol, ethylene glycol, diethylene glycol, etc. Itis further preferred that the sparging is performed under a vacuum,preferably a vacuum in the range of 5 to 500 mmHg. It is furtherpreferred that the sparging is performed for at least 30 minutes, morepreferably at least 90 minutes. It is further preferred that thesparging is performed at a temperature of about 50° C. to about 100° C.,more preferably at a temperature of 60° C. to about 70° C.

Upon completion of the reaction, the mixture is treated with a basicmaterial to form the glycidyl ether. The basic material is preferably astrong base such as a hydroxide. Preferred hydroxides include alkalimetal hydroxides with sodium being the typical choice. However, one ofordinary skill in the art will recognize that other basic materials mayalso be employed. The basic material is preferably added at levels offrom about 0.5 equivalents to about 2.5 equivalents, with about 0.95equivalents to about 2.0 equivalents being more preferred.

The product glycidyl ether may then be collected after optionalfiltration, drying and distillation according to the methods well-knownin the art.

To form the surfactant, an ethoxylated alcohol having the formula:

wherein R¹ and x are defined as before in an amount of from about 0.80to about 2.0 equivalents is combined with the metallic catalyst andheated to a temperature ranging from about 50° C. to about 95° C. andmore preferably from about 60° C. to about 80° C. when a Lewis acidcatalyst is employed. The glycidyl ether is then added to the mixtureand reacted for from about 0.5 hours to about 30 hours, more preferablyfrom about 1 hour to about 24 hours.

The metallic component of the catalyst is then extracted from theether-capped poly(oxyalkylated) alcohol surfactant product by at leastone aqueous extraction with an aqueous solution. The aqueous solution isselected from the group consisting of a from about 2% to about 15% byweight aqueous solution of sodium carbonate, a from about 2% to about10% by weight aqueous solution of potassium carbonate, a from about 1%to about 22% by weight aqueous solution of sodium sulfate, a from about2% to about 6% by weight aqueous solution of sodium bicarbonate, a fromabout 1% to about 10% by weight aqueous solution of potassium sulfate, afrom about 2% to about 24% by weight aqueous solution of potassiumbicarbonate, and mixtures thereof. The extraction may be either batch orcontinuous. It has surprisingly found that aqueous extractions withaqueous solutions containing salts, or combinations of salts other thanthose listed above do not reduce the metallic component of theether-capped poly(oxyalkylated) alcohol surfactant product. Examples ofunsuitable salts are sodium chloride, calcium carbonate, and sodiumhydroxide.

Multiple extractions of the ether-capped poly(oxyalkylated) alcoholsurfactant product may occur and are preferred. After the at least oneaqueous extraction the ether-capped poly(oxyalkylated) alcoholsurfactant product, contains less than about 100 ppm, preferably lessthan about 70 ppm, more preferably less than about 25 ppm, morepreferably less than about 10 ppm of the metallic component of themetallic catalyst.

A representative synthetic route is demonstrated via the followingdiagram and examples.

EXAMPLES 1. Preparation of C_(12/14)-alkyl-C_(11/15)-alkyl EthoxylatedEther Capped Alcohol Surfactant

Tergitol® 15-S-15 (150.0 g, 0.174 mol) is melted and added into a 500 mlfour-necked round bottom flask fitted with a condenser, nitrogen inlet,addition funnel, mechanical stirrer and internal thermometer. Thecontents of the flask are dried at 75° C. for 30 minutes under vacuum.An a nitrogen atmosphere is established. Stannic chloride (1.43 g) isadded to the flask via syringe. The mixture is heated to 85° C.C_(12 /14)-alkyl glycidyl ether (89.2 g, 0.348 mol) is added dropwiseover 1 hour, maintaining the reaction temperature. After stirring for anadditional 60 minutes at 75° C., the reaction is cooled to 60° C. thenquenched with the addition of 10 ml of water. The reaction productcontains 2100 ppm tin by elemental analysis.

Removal of Tin from Reaction Product of Example 1

1A. 15 g of 65° C. distilled water is added to a 125 ml separatoryfunnel followed by a 15 g aliquot of C_(12/14)-alkyl-C_(11/15)-alkylethoxylated ether capped alcohol from Example 1 above is preheated to65° C. Following moderate shaking, the organic and aqueous phases willnot separate.

1B. A solution containing 15% by weight sodium chloride in distilledwater is preheated to 65° C. A 15 g aliquot is added to a 125 mlseparatory funnel followed by a 15 g aliquot ofC_(12/14)-alkyl-C_(11/15)-alkyl ethoxylated ether capped alcohol fromExample 1 above is also preheated to 65° C. Following moderate shaking,the organic and aqueous phases will separate readily upon standing. Theorganic layer has a tin content of 2100 ppm by elemental analysis.

1C. A solution containing 15% by weight sodium carbonate in distilledwater is preheated to 65° C. A 15 g aliquot is added to a 125 mlseparatory funnel followed by a 15 g aliquot ofC_(12/14)-alkyl-C_(11/15)-alkyl ethoxylated ether capped alcohol fromExample 1 above is also preheated to 65° C. Following moderate shaking,the organic and aqueous phases will separate readily. The organic layerhas a tin content of 90 ppm by elemental analysis.

1D. The quenched reaction product obtained in Example 1, namely theC_(12/14)-alkyl-C_(11/15)-alkyl ethoxylated ether capped alcohol fromExample 1, is placed in a 125 ml separatory funnel. 15 g of a 65° C.solution of 15% by weight sodium carbonate in distilled water is thenadded to the funnel. Following moderate shaking, the organic and aqueousphases will separate upon standing. The organic layer has a tin contentof 90 ppm by elemental analysis.

Example 2

Tergitol® 15-S-15 (7517 g, 8.74 mol) is melted and added into a 22 Lthree necked round bottom flask fitted with a condenser, nitrogen inlet,addition funnel, mechanical stirrer and internal thermometer. Thecontents of the flask are dried at 75° C. for 2.5 hours utilizing anitrogen sparge. A nitrogen atmosphere is maintained. Stannic chloride(150 g) is added to the flask via syringe. The mixture is heated to 85°C. C_(12/14)-alkyl glycidyl ether (4467 g, 17.48 mol) is added dropwiseover 1 hour, maintaining the reaction temperature. After stirring for anadditional 60 minutes at 75° C., the reaction is cooled to 60° C. thenquenched with the addition of water (150 ml). The reaction productcontains 5000 ppm tin by elemental analysis.

Removal of Tin from Reaction Product of Example 2

2A. 15 g of the reaction product from Example 2 is extracted with anequal weight of a 5% aqueous solution of sodium carbonate by the methodgiven in example 1C. The layers separates in approximately 30 seconds.The organic layer contains 230 ppm tin. The resulting organic layer isthen extracted a second time with an equal weight of a 5% aqueoussolution of sodium carbonate. The layers separate in approximately 30seconds. The organic layer contains 15 ppm tin.2B. Following the methodof Example 2A, a 15% sodium chloride and 5% sodium hydroxide solution isused. The tin content of the organic layer is 2100 ppm.

2C. Following the method of Example 2A, a 5% solution of potassiumcarbonate is used. The tin content of the organic layer is 90 ppm.

2D. Following the method of Example 2A, a 5% solution of calciumcarbonate is used. The organic and aqueous phases will not separate uponstanding.

2E. Following the method of Example 2A, a 5% solution of sodium sulfateis used. The layers will separate in approximately 45 seconds uponstanding. The tin content of the organic layer is 69 ppm.

2F. Following the method of Example 2A, a 5% solution of sodiumbicarbonate is used. Phase separation occurs in approximately oneminute. The tin content of the organic layer is 23 ppm.

Example 3

12 kg of C_(12/14)-alkyl-C_(11/15)-alkyl ethoxylated ether cappedalcohol reaction product (5000 ppm tin) at 58° C. is added into a 20gallon stainless steel tank equipped with heating coils and a pitchedturbine mechanical agitator. 12 kg of 15% sodium carbonate solution at50° C. is added. The liquid contents are mixed for 5 minutes using theturbine mixer. The mixer is then shut off and the layers are allowed tosettle over a period of thirty minutes while the temperature ismaintained with hot water flow through the heating coil. The aqueouslayer is drained from the bottom leaving an organic layer with a tincontent of 71 ppm. A second extraction of the organic layer using 12 kgof 15% sodium carbonate solution at 50° C. is carried out. The tincontent of the organic layer following the second extraction is <10 ppm.

From the aforementioned surfactants, a cleaning composition, and inparticular, a dish or hard surface cleaning composition may be designed.The compositions can optionally include one or more other detergentadjunct materials or other materials for assisting or enhancing cleaningperformance, treatment of the substrate to be cleaned, or to modify theaesthetics of the detergent composition (e.g., perfume, colorants, dyes,etc.). The following are illustrative examples of such adjunctmaterials.

Detersive ingredients or adjuncts optionally included in the instantcompositions can include one or more materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or designed to improve the aesthetics of the compositions.Adjuncts which can also be included in compositions of the presentinvention, at their conventional art-established levels for use(generally, adjunct materials comprise, in total, from about 30% toabout 99.9%, preferably from about 70% to about 95%, by weight of thecompositions), include other active ingredients such as phosphate andnon-phosphate builders, chelants, enzymes, dispersant polymers (e.g.,from BASF Corp. or Rohm & Haas), color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, silicates, dyes, fillers,germicides, alkalinity sources, hydrotropes, anti-oxidants, enzymestabilizing agents, perfumes, solubilizing agents, carriers, processingaids, pigments, and pH control agents.

Depending on whether a greater or lesser degree of compactness isrequired, filler materials can also be present in the instantcompositions. These include sucrose, sucrose esters, sodium sulfate,potassium sulfate, etc., in amounts up to about 70%, preferably from 0%to about 40% of the composition. Preferred filler is sodium sulfate,especially in good grades having at most low levels of trace impurities.

Sodium sulfate used herein preferably has a purity sufficient to ensureit is non-reactive with bleach; it may also be treated with low levelsof sequestrants, such as phosphonates or EDDS in magnesium-salt form.Note that preferences, in terms of purity sufficient to avoiddecomposing bleach, applies also to pH-adjusting component ingredients,specifically including any silicates used herein.

The compositions of the invention can optionally contain an alkylphosphate ester suds suppressor, a silicone suds suppressor, orcombinations thereof. Levels in general are from 0% to about 10%,preferably, from about 0.001% to about 5%. However, generally (for costconsiderations and/or deposition) preferred compositions herein do notcomprise suds suppressors, that is they are totally free of them, orcomprise suds suppressors only at low levels, e.g., less than about 0.1%of active suds suppressing agent.

Hydrotrope materials such as sodium benzene sulfonate, sodium toluenesulfonate, sodium cumene sulfonate, etc., can be present, e.g., forbetter dispersing surfactant.

Bleach-stable perfumes (stable as to odor); and bleach-stable dyes suchas those disclosed in U.S. Pat. No. 4,714,562, Roselle et al, issuedDec. 22, 1987 can also be added to the present compositions inappropriate amounts.

Since the compositions can contain water-sensitive ingredients oringredients which can co-react when brought together in an aqueousenvironment, it is desirable to keep the free moisture content at aminimum, e.g., 7% or less, preferably 5% or less of the compositions;and to provide packaging which is substantially impermeable to water andcarbon dioxide. Coating measures may be employed to protect theingredients from each other and from air and moisture. Plastic bottles,including refillable or recyclable types, as well as conventionalbarrier cartons or boxes are another helpful means of assuring maximumshelf-storage stability. As noted, when ingredients are not highlycompatible, it may further be desirable to coat at least one suchingredient with a low-foaming nonionic surfactant for protection. Thereare numerous waxy materials which can readily be used to form suitablecoated particles of any such otherwise incompatible components; however,the formulator prefers those materials which do not have a markedtendency to deposit or form films on dishes including those of plasticconstruction.

The following nonlimiting examples further illustrate compositions ofthe present invention.

Example 4

An automatic dishwashing detergent composition is prepared as follows:

Weight % Ingredients: A B Sodium Tripolyphosphate (STPP) 24.0 45 Sodiumcarbonate 20.0 13.5 Hydrated 2.0r silicate 15 13.5 Nonionic surfactants¹2.0 2.0 Tergitol 15S9 Nonionic surfactant² 1.0 1.0 Polymer³ 4.0 —Protease (4% active) 0.83 0.83 Amylase (0.8% active) 0.5 0.5 Perboratemonohydrate (15.5% Active AvO)⁴ 14.5 14.5 Cobalt catalyst⁵ 0.008 —Water, sodium sulfate and misc. Balance Balance ¹Ether-cappedpoly(oxyalkylated) alcohol of EXAMPLE 1C ²Ethoxylated secondary alcoholsupplied by Union Carbide (cloud point = 60° C.). ³Terpolymer selectedfrom either 60% acrylic acid/20% maleic acid/20% ethyl acrylate, or 70%acrylic acid/10% maleic acid/20% ethyl acrylate. ⁴The AvO level of theabove formula is 2.2%. ⁵Pentaamineacetatocobalt(III) nitrate.

The ADD's of the above dishwashing detergent composition examples may beused to wash lipstick-stained plastic and ceramic, tea-stained cups,starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, starch,cheese, egg or babyfood-soiled flatware, and tomato-stained plasticspatulas by loading the soiled dishes in a domestic automaticdishwashing appliance and washing using either cold fill, 60° C. peak,or uniformly 45-50° C. wash cycles with a product concentration of theexemplary compositions of from about 1,000 to about 10,000 ppm, withexcellent results.

The following examples further illustrate phosphate built ADDcompositions which contain a bleach/enzyme particle, but are notintended to be limiting thereof. All percentages noted are by weight ofthe finished compositions, other than the perborate (monohydrate)component, which is listed as AvO.

Examples 5-6

5 6 Catalyst¹ 0.008 0.004 Savinase ™ 12T — 1.1 Protease D 0.9 —Duramyl ™ 1.5 0.75 STPP 31.0 30.0 Na₂CO₃ 20.0 30.5 Polymer² 4.0 —Perborate (AvO) 2.2 0.7 Dibenzoyl Peroxide 0.2 0.15 2 R Silicate (SiO₂)8.0 3.5 Paraffin 0.5 0.5 Benzotriazole 0.3 0.15 Nonionic surfactant³ 1.01.0 Sodium Sulfate, Moisture Balance ¹Pentaamineacetatocobalt (III)nitrate; may be replaced by MnTACN. ²Polyacrylate or Acusol 480N orpolyacrylate/polymethacrylate copolymers. ³A nonionic surfactantprepared according to EXAMPLE 2C.

In Compositions of Examples 6 and 7, respectively, the catalyst andenzymes are introduced into the compositions as 200-2400 microncomposite particles which are prepared by spray coating, fluidized bedgranulation, marumarizing, prilling or flaking/grinding operations. Ifdesired, the protease and amylase enzymes may be separately formed intotheir respective catalyst/enzyme composite particles, for reasons ofstability, and these separate composites added to the compositions.

Examples 7-8

Granular dishwashing detergents are as follows:

7 8 Composite Particle 1.5 0.75 Savinase ™ 12T 2.2 — Protease D — 0.45STPP 34.5 30.0 Na₂CO₃ 20.0 30.5 Acusol 480N 4.0 — Perborate (AvO) 2.20.7 2 R Silicate (SiO₂) 8.0 3.5 Paraffin — 0.5 Benzotriazole — 0.15Nonionic surfactant¹ 1.0 1.0 LF404² 1.0 0.75 Sodium Sulfate, Moisture tobalance ¹Prepared according to EXAMPLE 3. ²A blend ofethoxylated/propoxylated nonionic surfactants available from BASF.

Example 9

Light-duty liquid dishwashing detergent formulae are prepared asfollows:

Composition A B C Ingredient % Weight Surfactant¹ 1.00 2.00 1.50 AES32.00 33.00 29.00 Amine Oxide Surfactant 5.00 4.50 6.00 BetaineSurfactant 3.00 5.00 1.75 Perfume 0.18 0.18 0.18 Water and minorsBalance ¹Prepared according to EXAMPLE 1D

Example 10

An automatic dishwashing detergent tablet is prepared from thecomposition as follows:

Weight % Ingredients: A B Sodium Tripolyphosphate (STPP) 50.0 47.0Sodium carbonate 14.0 15 Hydrated 2.0r silicate 8.0 5.0 Nonionicsurfactant¹ 0.4 2.0 Tergitol 15S9 Nonionic surfactant² 1.0 1.0 Polymer³4.0 — Protease (4% active) 2.0 1.50 Amylase (0.8% active) — 0.5Perborate monohydrate (15.5% Active AvO)⁴ 1.5 1.5 Cobalt catalyst⁵ 0.008— TAED — 2.2 Benzotriazole 0.3 — Paraffin Oil⁶ 0.5 — Water, sodiumsulfate and misc. Balance Balance ¹Ether-capped poly(oxyalkylated)alcobol of EXAMPLE 2E ²Ethoxylated secondary alcohol supplied by UnionCarbide (cloud point = 60° C.). ³Polyacrylate polymer blended with HEDP.⁴The AvO level of the above formula is 2.2%.⁵Pentaamineacetatocobalt(III) nitrate. ⁶Winog 70 available fromWintershall, Salzbergen, Germany.

The ADD's of the above dishwashing detergent composition examples may beused to wash lipstick-stained plastic and ceramic, tea-stained cups,starch-soiled and spaghetti-soiled dishes, milk-soiled glasses, starch,cheese, egg or babyfood-soiled flatware, and tomato-stained plasticspatulas by loading the soiled dishes in a domestic automaticdishwashing appliance and washing using either cold fill, 60° C. peak,or uniformly 45-50° C. wash cycles with a product concentration of theexemplary compositions of from about 1,000 to about 10,000 ppm, withexcellent results.

Example 11

A hard surface cleaning composition according to the present inventionis illustrated as follows

Weight % Ingredients A B C D E F Surfactant¹  0.25 3.5 5.5 6.5  6.1 9.5Sodium hypochlorite 0.9 1.4 1.4 — — — Calcium hypochlorite — — — 0.5 — —Sodium dichlorocyanurate — — — —  1.2 2.0 Tetrapotassium pyrophos. 6.0 —— — 13.0 — Tripotassium phosphate 2.0 — — — 12.0 — Sodiumtripolyphosphate — — — 1.6 — — Calcium carbonate — — — — 39.0 1.1Calcium oxide — — — —  2.8 — Perlite abrasive 6.5 — — — 22.5 0.5 Sodiumhydroxide 0.8 1.6 1.8 0.8  1.1 1.0 Potassium hydroxide — — —  0.85 — —Dyes  0.75  0.28  0.28  0.28 — — Lanolin — — — — — 2.1Carboxymethylcellulose — — — — — 2.6 Water/Misc. bal. bal. bal. bal.bal. bal. ¹Ether-capped poly(oxyalkylated) alcohol of EXAMPLE 2E.

Example 12

Liquid gel-like automatic dishwashing detergent compositions accordingto the present invention as prepared as followed:

A B STPP builder 17.5 16 K carbonate 8 — Na carbonate — 1.5 K hydroxide2 2.0 K silicate 4 1.5 Na silicate 2 3 thickener 1 1 Nitric acid 0.020.02 Al tristearate 0.1 — polymer dispersant² 0.5 — Na benzoate 0.8 0.5Surfactant¹ 1.0 2.0 Perborate 2.2 Na hypochlorite 1.5 — Water and Minorsbalance balance ¹Ether-capped poly(oxyalkylated) alcohol of EXAMPLE 2F²sodium polyacrylate of 4500 m.w.

What is claimed is:
 1. A process for preparing an ether-cappedpoly(oxyalkylated) alcohol surfactant having the formulaR¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR² wherein R¹ and R² are linear orbranched, saturated or unsaturated, aliphatic or aromatic hydrocarbonradicals having from 1 to about 30 carbon atoms; R³ is H, or a linearaliphatic hydrocarbon radical having from 1 to about 4 carbon atoms; xis an integer having an average value from 1 to about 30; furtherwherein R² can optionally be alkoxylated, wherein said alkoxy group isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; said process comprising the steps of: (a) providing aglycidyl ether having the formula:

wherein R² is defined as above; (b) providing an ethoxylated alcoholhaving the formula:

wherein R¹, R³ and x are defined as above; (c) reacting said glycidylether with said ethoxylated alcohol to form said surfactant in thepresence of a metallic catalyst; (d) said surfactant is sparged with aninert gas; and (e) extracting said catalyst from said surfactant by atleast one aqueous extraction with an aqueous solution, wherein saidaqueous solution is selected from the group consisting of a from about2% to about 15% by weight aqueous solution of sodium carbonate, a fromabout 2% to about 10% by weight aqueous solution of potassium carbonate,a from about 1% to about 22% by weight aqueous solution of sodiumsulfate, a from about 2% to about 6% by weight aqueous solution ofsodium bicarbonate, a from about 1% to about 10% by weight aqueoussolution of potassium sulfate, a from about 2% to about 24% by weightaqueous solution of potassium bicarbonate, and mixtures thereof; andwherein said surfactant, after said at least one aqueous extraction,contains less than about 100 ppm of the metallic component of saidmetallic catalyst.
 2. The process as claimed in claim 1 wherein when xis about 2 or greater, R³ may be the same or different.
 3. The processas claimed in claim 1 wherein when x is about 15 or greater and when R³is selected from H and methyl, then at least four of the R³ groups aremethyl radicals; further wherein when x is about 15 or greater and whenR³ is selected from H and from 1 to 3 methyl groups, then at least oneR³ is ethyl, propyl or butyl.
 4. The process as claimed in claim 1wherein R¹ and R² are a linear or branched, saturated or unsaturated,aliphatic hydrocarbon radical having from about 6 to about 22 carbonatoms.
 5. The process as claimed in claim 1 wherein x is an integerhaving an average value of from about 6 to about
 15. 6. The process asclaimed in claim 1 wherein said metallic catalyst is a Lewis acidselected from the group consisting of SnCl₄, TiCl₄, Ti(O^(i)Pr)₄, ZnCl₂,SnCl₂, FeCl₃, BF₃, AlCl₃, and mixtures thereof.
 7. The process asclaimed in claim 6 wherein said metallic catalyst is a Lewis acidselected from the group consisting of SnCl₄, BF₃, AlCl₃, and mixturesthereof.
 8. The process as claimed in claim 1 wherein said surfactantafter said aqueous extraction contains less than about 70 ppm of themetallic component of said metallic catalyst.
 9. The process as claimedin claim 1 wherein said surfactant is sparged with an inert gas, undervacuum in the range of 5 to 500 mmHg.
 10. The process as claimed inclaim 1 wherein said catalyst is a Lewis acid catalyst and said step ofreacting glycidyl ether with ethoxylated alcohol is conducted at atemperature of from about 50° C. to about 95° C.
 11. The process asclaimed in claim 10 wherein said temperature ranges from about 60° C. toabout 80° C.
 12. The process as claimed in claim 1 wherein said step ofproviding said glycidyl ether further comprises the step of reacting alinear or branched, aliphatic or aromatic alcohol having the formulaR²OH and an epoxide having the formula:

wherein R² is defined as above and X is a leaving group.
 13. The processas claimed in claim 1 wherein said catalyst is a Lewis acid catalyst andsaid catalyst is employed at levels of from about 0.1 mol % to about 2.0mol %.
 14. The process as claimed in claim 13 wherein said step ofreacting a linear alcohol with an epoxide is conducted in the absence ofa solvent.
 15. The process as claimed in claim 13 wherein said step ofreacting a linear alcohol with an epoxide is conducted at about 40° C.to about 90° C.
 16. A process for preparing an ether-cappedpoly(oxyalkylated) alcohol having the formulaR¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR² wherein R¹ and R² are linear orbranched, saturated or unsaturated, aliphatic or aromatic hydrocarbonradicals having from 1 to about 30 carbon atoms; R³ is H, or a linearaliphatic hydrocarbon radical having from 1 to about 4 carbon atoms; xis an integer having an average value from about 6 to about 15; furtherwherein R² can optionally be alkoxylated, wherein said alkoxy group isselected from the group consisting of ethoxy, propoxy, butoxy andmixtures thereof; said process comprising the steps of: (a) forming aglycidyl ether having the formula:

wherein R² is defined as above by reacting a linear or branched,aliphatic or aromatic alcohol having the formula R²OH and an epoxidehaving the formula:

wherein R² is defined as above and X is a leaving group; (b) providingan ethoxylated alcohol having the formula:

wherein R¹, R³and x are defined as above; and (c) reacting said glycidylether with said ethoxylated alcohol to form said surfactant in thepresence of a metallic catalyst; (d) said surfactant is sparged with aninert gas; and (e) extracting said catalyst from said surfactant by atleast one aqueous extraction with an aqueous solution, wherein saidaqueous solution is selected from the group consisting of a from about2% to about 15% by weight aqueous solution of sodium carbonate, a fromabout 2% to about 10% by weight aqueous solution of potassium carbonate,a from about 1% to about 22% by weight aqueous solution of sodiumsulfate, a from about 2% to about 6% by weight aqueous solution ofsodium bicarbonate, a from about 1% to about 10% by weight aqueoussolution of potassium sulfate, a from about 2% to about 24% by weightaqueous solution of potassium bicarbonate, and mixtures thereof; andwherein said surfactant, after said at least one aqueous extraction,contains less than about 100 ppm of the metallic component of saidmetallic catalyst.
 17. The process as claimed in claim 1 wherein when xis about 6 or greater, R³ may be the same or different.
 18. The processas claimed in claim 1 wherein when x is about 15 and when R³ is selectedfrom H and methyl, then at least four of the R³ groups are methylradicals; further wherein when x is about 15 and when R³ is selectedfrom H and from 1 to 3 methyl groups, then at least one R³ is ethyl,propyl or butyl.
 19. The process as claimed in claim 16 wherein saidsurfactant after said aqueous extraction contains less than about 70ppmof the metallic component of said metallic catalyst.
 20. The process asclaimed in claim 16 wherein said step of reacting glycidyl ether withethoxylated alcohol is conducted at a temperature of from about 50° C.to about 95° C.
 21. The process as claimed in claim 16 wherein saidmetallic catalyst is a Lewis acid selected from the group consisting ofSnCl₄, TiCl₄, Ti(O¹Pr)₄, ZnCl₂, SnCl₂, FeCl₃, BF₃, AlCl₃, and mixturesthereof.
 22. The process as claimed in claim 16 wherein said metalliccatalyst is a Lewis acid selected from the group consisting of SnCl₄,BF₃, AlCl₃, and mixtures thereof.